Manufacture of soap from marine oils



Patented Nov. 23, 1931 UNITED STATES PATENT oFrici: I Masonic-rune215g;- raoriimirmn I Sigval Schmidt-Nielsen, Trondhjem, and Arne .Flood,Larvik, Norway No Drawing. Application November 2,1936, Serial No.108,900. In Norway June 20, 1933 4 Claims.

This invention relates to the manufacture of soap from marine oils andhas for its object a process by means of which it is made possible fromsuch oils to obtain soaps of good lathering 5 quality permanently freefrom the disagreeable fishy odors usually inherent .in soapsmanufactured from marine oils. I

This application is a continuation-impart of of our copendingapplication Serial No. 730,841

lessen their oxidizability. a

An important feature of thepresent invention consists therein, that themarine oils prior to the saponiflcation operation are subjected to atreatment by which the autooxidizability of the oils is eliminatedorreduced without the aid of added oxygen, hydrogen or other elements andwithout simultaneous polymerization to any substantial degree. Accordingto the invention this change vin the character of the oils is the-resultof an intramolecular saturation of the oil brought about by heating forseveral days in closed vessels under pressure at temperatures betweenabout 250 C. and 300 C. A necessary condition to bring.

about the said interior saturation of the fat molecule is that the saidheat treatment is extended over a period of considerably more han 48hours, preferably about 72 hours or more.

It has been found that by maintaining a temperature not substantiallyabove 250-260 during the main part of the heat treatment it is possibleto-bring about the said intramolecular saturation without appreciablepolymerization. When an oil obtained according to the invention isdecom- 35 posed to obtain the fatty acids thereof in a free condition itwill be found that these acids are capable of being distilled with watervapour. As well known this is not the case with fatty acids ofpolymerized oils. The fact that the decrease of the iodine number hasbeen effected by intramolecular saturation and not principally bypolymerization can also be ascertained by conventional molecular weightdetermination.

The heat treatment according to the invention will produce the resultsabove referred to without the aide! any foreign additions. The treat.-ment takes place in closed vessels with consequent pressure and there isno loss of substance. A small quantity of water is formed as aconsequence of the intramolecular saturation, and the percentage of freeaclds in the oil is increased at the same time as the percentage ofunsaponiflable matter increases owing to the formation of hydrocarbons.

As is well known,

'filedJune 15, 1934 for the Treatment of oils to the of oils and fatspro-- duced from marine animals (fishes, whales, seal and the like) ishighly limited owing to the autooxidizability. This property of the oilsis due to the fact that the molecules of the compounds, of which theoils are composed, comprise a great 5 number of'double bonds. If thesedouble bonds are not eliminated, the marine oils will retain their highdegree of 'autooxidizability and consequently their restricted field ofuse. In the manufacture of soaps the odor can be dis- 10 guised by theaid of perfumes, but sooner or later it reappears in the washedmaterials (laundry, etc.).

It is known that it is possible to add hydrogen, oxygen, sulphur andother elements or radicals .15 to the oils (or fats) and that inthis-manner stable oils or fats may be obtained. A great number ofpatents have therefore been issued which deal with thetreatment offatsor fatty acids respectivelywith hydrogen, the socalled 'oilhardeningtreatment as well as with the polymerization of fats or fatty acids byheating to elevated temperatures in the presence of air resulting in apowerful oxidation simultaneously with polymerization andanhydrideformation.

It has also been suggested (U. S. A. Patent No. 1,151,002) to improvethe quality of soaps made i from marine oils by subjecting the oils to acombined polymerization and hydrogenation treatment because it has beenfound that by inter- 3o posing the polymerizing treatment the producedsoaps vwill be of a more satisfactory lathering quality than soapsproduced from ordinary hydrogenated marine oils. 1

According to the present invention no hydrogenation treatment isrequired, the desired results being obtained solely by extending theheat treatment under pressure over a period of several days.

By thistreatment the desirable decrease of the 40 iodine number isattained neither by the addition of hydrogen or other foreign substancesnor by polymerization but by an intramolecular saturation of the doublebonds of the oil molecules.

The oils treated according to the invention will be found to haveacquired a pleasant smell and taste as well as a lighter colour and arean excellent raw material for the manufacture of soaps of any kind.

The duration of the heat treatment required v to produce the effectsaimed at will to some degree depend on the temperature employed, thecharacter of the oils, the pressures employed as well as on theconditions of operations in general. But usually several days durationof the as heat treatment will be necessary when ordinary The temperaturemay be maintained constant during the entire reaction period, or thetem-' perature may be caused to rise or sink respectively in stages. Andit may also sometimes be suitable to carry the heat treatment intoefiect in several stages separated from one another by periods withlowered temperatures.

It is not required to subject the crude oils to I any .preparatorytreatment with the object of removing water or protein-matter. And it isusually preferred to subject the oils or fats in a crude condition tothe heat treatment according to the invention.

A possibly desired, refining of the oils ,for example to removecolouring matter may be carried out subsequent to the heat treatmentherein referred to.

Example Ordinary medicinal cod liver oil was heated in aclosed'co'ntainer (autoclave) under nitrogen for about 72 hours at 250C. By this treatment the iodine number was lowered from 170 to 84. Theresulting oil was of lighter colour than the initial material and hadattained a slightly aromatic smell. The oil had lost every trace of theoriginal taste and smell of cod liver oil. The hexabromide test gave anegative result. The saponification number was unaltered as also theaverage molecular weight (determined by the camphor meth- 0d). The oilreacted readily with lye and produced an entirely white soa Example 2Crude whale oil No. 0-1 was heated in nitrogen atmosphere in a closedautoclave for about hours at 250 C. In the course of the treatment theiodine number fell from 112 to 76. The oil behaved as indicated inExample 1. The resulting oil was then subjected to the'conventionalsaponification treatment without any preparatory refining treatment.

Example 3 Whale oil No. 0-1 was heated in nitrogen atmosphere in aclosed container to about 260 C. for about 72 hours. Owing to localoverheating, the colour of the treated oil was somewhat darker than ofthe initial material. It reacted readily with saponification lye. Bysalting out a light, hard soap and a quite light under liquor suitablefor glycerine production resulted. In spite of the fact that noadditions were used, the finally obtained soap had a pleasant smell. Itcould be readily pressed to blocks as is the case with other grain soap.By the addition of small proportions of other fats, the soap could bemade into prepared toilet soaps (pilierte Toiletten-Seifen).

Example 4 L Whale oil No. 4 was heated. in a closed vessel to about 260C. for 72 hours.

In the course of this treatment, the iodine number fell from 102 to 65.The resulting oil was of a somewhat lighter colour than the initial oiland was slightly fluorescent. At room temperature it was of abutter-like semisolid consistency. It produced a dark coloured soap ofagreeable smell. In manufacturing practice it would be advisable tosubject an oil of the character obtained according to this example to ableaching treatment before use as a raw material for fine soaps.

We claim:

1. Process for the manufacture of soaps from unoxidized andunhydrogenated marine oils comprising the step of heating the marineoils without adde'd catalysts and in the absence of oxygen marine oil issubjected to the heat treatment in a crude condition.

4. Process for the manufacture of soaps from unoxidized andunhydrogenated marine oils comprising the step of heating the marineoils without added catalysts and in the absence of oxygen to atemperature between about 250 C. and 260 C. in closed vessels, the saidheating being continued for a period of time not less than 48 hoursdecrease of the so as to bring about a substantial decrease of theiodine number by intramolecular saturation of the glyceride moleculesand subjecting the resulting product to saponification by the aid'ofadded alkali. v

SIGVAL SCHMIDT-NIELSEN. ARNE FLOOD.

